title: Entropy-driven rearrangement of the water network at the hydrated amide group of the trans-formanilide-water cluster in the gas phase.
abstract: Photoionization-induced rearrangement of the water network in the trans-formanilide 1:4 cluster, FA-(H(2)O)(4), has been investigated by using IR-photodissociation spectroscopy and quantum chemical calculations. The IR spectrum of FA-(H(2)O)(4) in the S(0) state shows that the observed cluster has a cyclic hydrogen-bonded structure where the CO group and the NH group of FA are bridged with four water molecules, consistent with the reported structure [E. G. Robertson, Chem. Phys. Lett., 2000, 325, 299]. However, the corresponding cyclic hydrogen-bonded structure in the D(0) state of [FA-(H(2)O)(4)](+) is a minor product arising from photoionization via the S(1)-S(0) origin of FA-(H(2)O)(4). The dominant product has an extended H-bonded structure, where the intermolecular hydrogen bond between the hydrogen of the OH group of a water molecule and the CO group is dissociated. This is the first observation of a photoionization-induced rearrangement of the water network in [FA-(H(2)O)(4)](+). Through DFT calculations, we conclude that the rearrangement occurs due to entropic effects.
authors.affiliation: Department of Chemistry, Faculty of Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan.
authors.forename: Kenji
authors.initials: K
authors.lastname: Sakota
authors.forename: Yuiga
authors.initials: Y
authors.lastname: Shimazaki
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Sekiya